Benzoxanthene and benzothioxanthenedicarboxylic acid triazinyl-imide dyestuffs

ABSTRACT

BENZOXANTHENE- AND BENZOTHIOXANTHENE-DICARBOXYLIC ACID IMIDE DYESTUFFS OF THE GENERAL FORMULA   1,3-DI(O=),2-R,5-R3,11-R4,R1,R2-ANTHRA(2,1,9-DEF)ISO-   QUINOLINE WHERE C6 IS X   WHEREIN X IS OXYGEN OR SULFUR, R IS AMINO WHICH IS SUBSTITUTED BY ONE OR TWO MEMBERS OF THE GROUP OF ALKYL, CYCLOHEXYL, BENZYL, ACYL, PHENYL, B-CYANOETHYL, B-HYDROXYETHYL, SULFAMIDOPHENYL, BENZOYL, DICHLOROBENZOYL, SULFAMIDOBENZOYL, CARBOXAMIDOPHENYL, PHENYLSULFONYL SULFAMIDODICHLOROBENZOYL, CHLOROPHENYL, PHENOXYACETYL LOWER ALKYYLSULFAMIDOBENZOYL AND BENZIMIDAZOYL, OR 2,4,6-TRIAMINOTRIAZINYL, 2,4-DIAMINO-6-PHENYLTRIAZINYL, 2,4-DIAMINO-6-LOWER ALKYL TRIAZINYL-2,4-DIAMINO-6-HYDROXY LOWER ALKYL TRIAZINYL, 2,4-DIAMINO-6-CHLORO LOWER ALKYL TRIAZINYL, 2,4DIAMINO-6-PHENYLAMINO TRIAZINYL, 2,4-DIAMINO-6-LOWER ALKOXY LOWER ALKOXY TRIAZINYL, 2,4-DIAMINO-6-BENZOYLTRIAZINYL, R1 AND R2 AREHYDROGEN, CHLORINE, BROMINE, CYANO, LOWER CARBALKOX, LOWER ALKYL, LOWER ALKOXY AND PHENYL, R3 AND R4 ARE HYDROGEN, LOWER ALKXOY AND LOWER HYDROXY ALKOXY.

Ufiit'd sates" Patent 3,748,330 Patented July 24, 1973 3,748,330 BENZOXANTHENE AND BENZOTHIOXANTHENE- DICARBOXYLIC ACID TRIAZINYL-IMIDE DYE- STUFFS Otto Fuchs and Helmut Troster, Frankfurt am Main,

Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany No Drawing. Filed Apr. 13, 1971, Ser. No. 133,755 Claims priority, application Germany, Apr. 14, 1970, P 20 17 763.3 Int. Cl. C07d 55/18, 55/22 U.S. Cl. 260249.6 7 Claims ABSTRACT OF THE DISCLOSURE Benzoxantheneand benzothioxanthene-dicarboxylic acid imide dyestuffs of the general formula wherein The present invention relates to valuable novel benzoxanthene and benzothioxanthene dicarboxylic acid amide dyestuffs of the general formula in which X represents an oxygen or sulfur atom,

R represents an amino group substituted by an optionally substituted alkyl, cycloalkyl, aralkyl, acyl or aryl group or a heterocyclic radical, or a 1,3,5-triazinyl radical substituted by unsubstituted or substituted amino groups or by alkyl, hydroxy-alkyl, alkoxyalkyl, halogenoalkyl, aralkyl, aryl or heterocyclic groups,

R and R each represents a hydrogen atom, a halogen atom, especially a chlorine or bromine atom, a cyano group, a carbalkoxy group, for example, a carbomethoxy group, an alkyl, alkoxy or aryl group,

R represents a hydrogen atom or an alkoxy group which may be substituted, for example, by a halogen atom, a hydroxy, alkoxy, acyloxy or aryl group, and

R represents a hydrogen atom or, being equal to R an optionally substituted alkoxy group.

The novel dyestuffs of the above Formula 1 are obtained by condensing benzoxanthene or benzothioxanthene-3,4-dicarboxylic acid anhydrides of the general formula in which Formulae 2 and 3 X, R, R R R and R are defined as above, at a temperature within the range of from to 280 C. The dyestuffs, in which R of the'General Formula 1 stands for an optionally substituted acylamino group, may also be obtained by reacting benzoxanthene or benzothioxanthene-3,4dicarboxylic acid hydrazides of the general formula at a temperature within the range of from about 50 to about 200 C. with carboxylic acid halides or anhydrides of the general formula R'COY (R'co),0

or sulfonic acid halides of the general formula RSO Y X, R R R and R of the cited Formula 4 being as defined above, R of the cited Formulae 5, 6 and 7 representing an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group and Y of the cited Formulae and 7, representing a halogen atom, for example a chlorine or bromine atom.

In the case where R of the cited Formula 3 stands for a substituted amino group, the benzoxanthene or benzothioxanthene-S,4-dicarboxylic acid anhydrides of the Formula 2 are advantageously heated, optionally under pressure, preferably at 120220 C., with at least equirnolar, preferably excess, amounts of the corresponding compound of the Formula 3, optionally in an inert solvent and/or diluent, for example water, ethanol, ethyleneglycol monoalkyl ethers or dimethylformamide, furthermore in higher-boiling aromatic hydrocarbons, for example chloro-, dichloroor trichlorobenzene, tl-Chlol'o' naphthalene, or in quinoline or pyridine, for a prolonged period.

Advantageously, acid condensation agents, for example, zinc chloride, zinc acetate or the corresponding cadmium salts, as well as acetic acid, toluene-sulfonic acid, hydrochloric acid, sulfuric acid or phosphoric acid, are added, the condensation agent chosen depends on the solvent or diluent used.

The dyestufis formed precipitate from the reaction mixture and may be isolated in known manner.

In the case where R of the cited Formula 3 stands for a substituted 1,3,5-triazinyl radical, condensation with the anhydride of Formula 2 is advantageously carried out, preferably at a temperature within the range of from 180 to 240 C., in a high-boiling solvent, such as quinoline or nitrobenzene in the presence of acid condensation agents, for example, zinc chloride, zinc acetate or zinc tosylate or the corresponding cadmium salts.

The dyestulfs isolated in known manner may optionally be freed from unreacted amino triazine or anhydride by treating them with dilute acid or dilute alkaline solution.

Acylation of benzoxanthene or benzothioxanthene-3,4- dicarboxylic acid hydrazides of the Formula 4 may be carried out with equimolar or excess amounts of the acid halides or anhydrides of Formulae 5-7, whereupon monoor diacyl hydrazides or mixtures thereof are obtained.

The hydrazides (4) are advantageously heated, optionally under pressure, preferably at 70 to 150 (2., with the acylation agents of Formulae 5 to 7 optionally in an inert solvent and/or diluent, for example dimethyl-formamide, N-methyl-pyrrolidone, chloroor dichlorobenzene, pyridine or quinoline.

Suitable hydrazines of Formula 3 for the condensation with benzoxanthene or benzothioxanthene-3,4 dicarboxylic acid anhydrides are, for example,

p-cyano-ethyl hydrazine, p-hydroxy-ethyl hydrazine,

phenyl hydrazine,

4-chloro-phenyl hydrazine, 2,4-dichloro-phenyl hydrazine,

p-tolyl hydrazine,

B-rnethoxy-phenyl hydrazine, 4-hydrazino-benzamide,

3- and 4-hydrazinobenzene-sulfonamide, Z-hydrazino-S-sulfonamido-benzimidazole, Z-hydrazino-benzothiazole, Z-hydrazino-pyridine;

furthermore the hydrazides of stearic acid,

phenyl-acetic acid,

phenoxy-acetic acid,

benzoic acid,

2,4-diehloro-benzoic acid, 3-sulfonamido-benzoic acid, Z-hydroxy-S-sulfonamido-benzoic acid, 2,4-dichloro-5-sulfonamido-benzoic acid, 3-methylsulfonyl-benzoic acid, 2-hydroxy-4-methyl-benzoic acid,

3-hydroxy-diphenylene-oxide-2-carboxylic acid, benzene-sulfonic acid, 2,S-dichlorobenzene-sulfonic acid, p-toluene-sulfonic acid.

Suitable amino triazines are 2,4,6-triamino-1,3,5-triazine (melamine), 2,4-diamino-6-methyl-1,3,5-triazine, 2,4-diamino6-methylamino-1,3,5-triazine, 2,4-diamino-6- fi-hydroxyethyl) l, 3,5 -triazine, 2,4-diamino-(fi-ethoxyethyl) -1,3,5-triazine, 2,4-diamino-6-(chloroethyl)-l,3,5-triazine, 2,4-diamino-6-heptyl-1,3,S-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2-amino-4,6-diphenylamino-triazine and 2-amino-4,6-diphenyl triazine.

For the acylation of the hydrazides of Formula 4 there may also be used, in addition to the acid chlorides or acid bromides (Formula 5) or the carboxylic acid anhydrides (Formula 6) already mentioned with the acyl hydrazides, for example, also those of acetic acid or lauric acid, 4- sulfonamido-benzoic acid and the acid chlorides or bromides (Formula 7) of ethane-sulfonic acid, benzene-sub fonic acid, 2,S-dichlorobenzene-sulfonic acid, p-toluenesulfonic acid, 2-bromobenzene-sulfonic acid, 2,4,5-trimethylbenzene-sulfonic acid and 4-hydroxybenzene-sulfonic acid. The benzoxanthene-3,4-dicarboxylic acid anhydrides or hydrazides of the Formulae 2 or 4 (X=0) used as starting products may be obtained according to the processes described in Italian Pat. No. 863,081, the corresponding benzothioxanthene compounds (X=S) according to German Pat. No. 1,297,259 and British Pat. No. 1,112,726.

The novel compounds according to the invention are valuable, greenish yellow to orange fluorescent dyestulfs which are particularly suitable for the dyeing of condensate resins and synthetic polymers, such as polyvinyl chloride, polystyrene and polymethacrylate.

The most important dyestufis according to the present invention are those of Formula 1 in which X stands for an oxygen atom. On the materials mentioned above they produce greenish yellow to orange dyeings of intensely blue-green to yellow fluorescence, which are distinguished by a very good fastness to light and some of them, by high reflectance values.

The following examples serve to illustrate the invention:

EXAMPLE 1 31.8 g. of lO-methoxy-benzoxanthene-3,4-dicarboxylic acid anhydride, 24.2 g. of phenyl hydrazine and 5.0 g. of glacial acetic acid were refluxed for 7 hours. The dyestufi of the formula N-NH which precipitated in brilliant yellow crystals, was suction-filtered, washed with methanol and dried. It dyes polystyrene and polymethacrylate materials yellow with shades of intense green fluorescence and a good fastness to light. If, instead of phenyl hydrazine, equivalent amounts of 2,4-dichloro-, p-tolyl-, 3-methoxyphenyl hydrazine or Z-hydrazino-pyridine were used, dyestufis of similar properties were obtained.

EXAMPLE 2 A mixture of 14.4 g. of benzoxanthene-3,4-dicarboxylic acid anhydride, 5.0 of p-cyanoethyl hydrazine and ml. of methyl-glycol were kept boiling for 6 hours. After the reaction had been terminated the reaction mixture was cooled and the yellow dyestufif of the formula was isolated as indicated in Example 1. The compound produces brilliant greenish-yellow shades having a very good fastness to light on unplasticized polyvinyl chloride.

EXAMPLE 3 16.9 g. of 6-methoxybenzoxanthene-3,4-dicarboxylic acid anhydride were reacted at 135 to 140 C. for 6 hours in the autoclave in 380 ml. of ethanol with 4.5 g. of fi-hydroxyethyl hydrazine. The reaction product of the formula isolated in usual manner dyes polystyrene and polymethacrylate materials with yellow shades of yellow green fluorescence and a good fastness to light.

EXAMPLE 4 A mixture of 15.1 g. of 9-methylbenzoxanthene-3,4-dicarboxylic acid anhydride and 12.8 g. of 3-hydrazinobenzene-sulfonamido hydrochloride was stirred at 190 to 200 C. for 4 hours in 85 g. of quinoline while a slight nitrogen current was passed through. After cooling, the reaction mixture was diluted with 250 ml. of methanol, stirring was continued for several hours, and the precipitated dyestufl of formula down,

was suctionfiltered. It was washed with methanol and then with a large amount of boiling water and dried. This dyestulf can be used for dyeing condensate resins, for example on the basis of melamine formaldehyde, yellow shades of an intense green fluorescence and a good fastness to light, and a very good fastness to bleeding.

EXAMPLE 5 8.4 g. of 9 chloro-10-methylbenzoxanthene-3,4-dicarboxylic acid anhydride were refluxed for 6 hours with 4.0 g. of benzoic acid hydrazide in 80 g. of o-dichlorobenzene and 8.0 g. of quinoline in the presence of 0.5 g. of zinc chloride. After cooling, the reaction mixture was 6 diluted with g. of ethanol and the dyestuffs of formula N-NH-O o o-O was isolated in known manner. It dyes condensate resins, for example alcohol-modified melamine-formaldehyde resin materials in yellow shades of a green fluoroescence and a good fastness to light.

EXAMPLE 6 36.0 g. of benzoxanthene 3,4-dicarboxylic acid anhydride, 31.5 g. of 2,4,6-triaminotriazine and 12.5 g. of zinc acetate were introduced into 400 g. of quinoline. Then the mixture was heated at 220 to 235 C., while a slight nitrogen current was passed through, and it was maintained at this temperature for 3 hours. The yellow condensation product was subsequently suction-filtered at room temperature, washed with a small amount of quinoline, then with ethanol and water. The moist filter cake was subsequently treated for 30 minutes each with 300 ml. of boiling 5% hydrochloric acid and then with 300 ml. of boiling 2% potassium carbonate solution and worked up as usual. The dyestuif of formula was obtained in the form of a yellow powder. On commercial condensate resins, for example urea-formaldehyde resins this dyestufl produces yellow shades of an intense green fluorescence and a good fastness to bleeding.

EXAMPLE 7 15.9 g. of 9 methoxybenzoxanthene-3,4-dicarboxylic acid anhydride were kept boiling for 5 hours with 18.7 g. of 2,4-diamino-6-pheny1triazine in 160 g. of nitrobenzene while adding 5.0 g. of zinc acetate. The reaction mixture was diluted with ml. of ethanol after cooling and the dyestufi of formula was worked up as described in Example 6.

On condensate resins which are suitable for moulding compositions, for example urea-formaldehyde resins in powder form, shades of a green fluorescence and good fastness properties are obtained.

which crystallized while cooling, dyes polymethacrylate 2() materials in golden yellow shades of a green-yellow fluorescence and a very good fastness to light.

8 EXAMPLE 9 4.3 g. of 2,4-dichlorobenzoic acid chloride were introduced into a suspension of 7.2 g. of 6,10-dimethoxybenzoxanthene 3,4-dicarboxylic acid hydrazide in g. of quinoline and the mixture was stirred at to C. for 3 hours. The yellow reaction product of formula isolated in known manner is very suitable for dyeing polyvinyl chloride brilliant yellow shades.

The following tables shows further fluorescent greenish yellow to orange dyestnfis which are obtained according to the methods described in the above examples.

Example X R 3; Rs Rs R4 R5 Shade 10 0 NH: E H H H OCH; Yellow.

l NH 11 0 Bameasahove OCH; H H OH; H Golden yellow: 12 0 do H H H CH; CH; Yellow.

13 0 NH; H H H H H Yellow-green;

A -L N CHI 14. 6 Semeasabove.. OOH; H H Br H Yellow:

15 O NHCHaOIhOH OCH: H H H OCH; Orange plus yellow.

lNJNHa 16 0 Sameeeahove OCH; OCH; H H H Do:

17 O NHCHsCHzCI H H H Cl H Yellow plus green:

I NE:

18 0 (lg: H H OH: H H Yellow-green:

I NHC\ I 19 0 111 1 H H CH: OH: H Do:

1 1 We claim: 1. A benzoxantheneor benzothioxanthene-dicarboxylic acid triazinyi-imide dyestufi of the formula 2. A dyestuff according to claim 1 wherein X is O.

3. A dyestufi according to claim 1 wherein X is S.

4. A dyestuif according to claim 1 wherein X is 0, R is hydrogen, methyl, methoxy, chlorine or bromine, R is hydrogen or methyl, R is hydrogen or methoxy, and R is hydrogen or methoxy.

5. A dyestufi according to claim 1 wherein X is 0 and R" is amino.

6. A dyestulf according to claim 1 wherein X is 0, R R R and R each is hydrogen, and R and R" each is amino.

7. A dyestufi according to claim 1 wherein X is 0, R is methoxy, R R and R each is hydrogen, R is phenyl and R" is amino.

References Cited UNITED STATES PATENTS 3,357,985 12/1967 Fuchs et a1 260-4496 X 3,546,222 12/1970 Irving et a1. 260249.6

JOHN M. FORD, Primary Examiner US. Cl. X.R. 

